US10246545B2 - Bismuth-containing catalyst for polyurethane compositions - Google Patents

Bismuth-containing catalyst for polyurethane compositions Download PDF

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US10246545B2
US10246545B2 US14/359,666 US201214359666A US10246545B2 US 10246545 B2 US10246545 B2 US 10246545B2 US 201214359666 A US201214359666 A US 201214359666A US 10246545 B2 US10246545 B2 US 10246545B2
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bismuth
carbon atoms
group
containing catalyst
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Urs Burckhardt
Rita Cannas
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Sika Technology AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
    • C07C235/74—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to the field of polyurethane compositions and to catalysts for polyurethane compositions.
  • Polyurethane compositions have been known for quite some time and are employed in many areas. Traditionally, the expert community distinguishes between one-component and two-component polyurethane compositions. One-component polyurethane compositions cure on exposure to moisture. Two-component polyurethane compositions contain a curing agent as the second component, which essentially comprises polyamines and/or polyols. In both instances, isocyanate group-containing compounds or prepolymers are employed.
  • catalysts are admixed. While a plurality of polyurethane catalysts are known, the majority of them are not particularly selective with respect to the urethanization reaction, which is to say the reaction of alcohol OH groups with isocyanate groups, but generally also catalyze other reactions of the isocyanate group, such as allophanate and biuret formation or cyclotrimerization. In particular, the urethanization reaction typically competes with the reaction of the isocyanate groups with water, which results in urea groups with production of gaseous carbon dioxide.
  • the water responsible for the formation of bubbles either stems from the residual water content of the constituents of the composition, in particular the polyols and the fillers, which are generally moist even after drying processes and have a typical residual water content of 0.01 to 0.5% by weight, or from the ambient moisture, which penetrates into the composition by diffusion from the air or from the substrates, which occurs in particular in the case of high humidity, porous substrates and/or hydrophilic polyols, such as the polyether polyols frequently employed in practice.
  • the amine catalysts used extensively in practical applications such as tertiary amines
  • tin catalysts such as dialkyl tin carboxylates
  • the residual water content of the polyurethane composition additionally causes catalysts that are sensitive to hydrolysis, such as bismuth carboxylates, to become deactivated if the composition is kept for an extended period prior to use (storage), which adversely affects the curing speed and the mechanical properties.
  • catalysts that are sensitive to hydrolysis such as bismuth carboxylates
  • the resistance of the cured composition under thermal load is insufficient with some known catalysts, such as dialkyl tin carboxylates, the catalyst causing a decrease in the molecular weight, which is to say depolymerization, with loss of mechanical strength.
  • many of the known catalysts are solid at room temperature and poorly soluble in the polyurethane starting materials or the plasticizers, so that organic solvents must be used for their application in compositions that cure at room temperature.
  • many of the known catalysts in particular those based on heavy metal compounds, raise toxicological concern.
  • bismuth compounds as catalysts for curable compounds, such as polyurethane compositions
  • U.S. Pat. No. 4,584,362 describes the use of bismuth(III) tricarboxylates, such as bismuth-2-ethylhexanoate or bismuth neodecanoate. While such bismuth(III) tricarboxylates are characterized by very high catalytic activity with good selectivity with respect to the urethanization reaction, and additionally do not raise high toxicological concern, they are extremely sensitive to moisture and thus become rapidly deactivated during storage. While according to WO 2004/033519 and U.S. Pat. No.
  • WO 2009/050115 discloses organometallic catalysts, which are suitable for polyaddition or polycondensation reactions. Examples that are listed include bismuth(III) phenyl oxoacetate, bismuth(III) benzoyl benzoate and tris-(4-benzoyl-benzyloxy)-bismuth. Catalysts for polyurethane compositions are also known from JP-A-2005-068402.
  • the catalyst is to be characterized by high catalytic activity and selectivity with regard to the urethanization reactions, which is to say the reaction of alcohol OH groups with isocyanate groups, and thereby enable a rapid synthesis, which has the lowest possible interference from moisture, of a mechanically superior polyurethane polymer from polyfunctional alcohols (polyols) and polyisocyanates
  • the catalyst is to have sufficient hydrolysis resistance so as to remain intact under customary storage conditions, which is to say at room temperature or at slightly elevated temperatures, over several months in a residual water-containing polyol composition without any significant loss of activity.
  • the catalyst is to reduce the thermal resistance of the cured polyurethane polymer as little as possible.
  • the catalyst is to be liquid at room temperature or at slightly elevated temperatures and/or to be easily soluble in the polyurethane starting materials or in the plasticizers, so that it is easy to employ in solvent-free systems that cure at room temperature.
  • the catalyst is to have as low a toxicity as possible.
  • the catalyst is to have good thermal and hydrolytic stability, thus not hydrolyzing quickly in a residual water-containing polyol, and therefore to maintain the catalytic activity even with extended storage, and it is to be liquid at room temperature and/or have good solubility in plasticizers or polyols, so as to be easy to employ in systems that cure at room temperature, without the use of volatile organic solvents (VOCs).
  • VOCs volatile organic solvents
  • the catalyst is to be substantially colorless and should not become discolored even under the effect of light, so as to allow use thereof also in unpigmented or light-colored products without impairment.
  • This bismuth-containing catalyst can be obtained by reacting at least one bismuth(III) salt or bismuth(III) complex with at least one 1,3-ketoamide with the formula (I),
  • R 1 and R 2 independently of one another are a hydrogen group, a monovalent saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, or together are a bivalent alkylene group having 3 to 6 carbon atoms
  • R 3 and R 4 independently of one another are a hydrogen group, a monovalent saturated hydrocarbon group, which optionally includes heteroatoms, having 1 to 12 carbon atoms, or together are a bivalent alkylene group, which optionally includes heteroatoms, having 3 to 6 carbon atoms.
  • the stoichiometric ratio between the bismuth(III) salt or the bismuth(III) complex and the 1,3-ketoamide with the formula (I) preferably ranges between approximately 1:0.5 and 1:20, particularly preferably between 1:1 and 1:10, and most preferably between 1:3 and 1:6. This results in the advantage that the catalyst exhibits good stability to hydrolysis and also high catalytic activity.
  • the ligand can be mapped in various mesomeric structures, such as the resonance structures described hereafter. All possible resonance structures of the ligand L with the formula (I) are regarded to be equivalent within the context of the present invention.
  • R 1 and R 2 independently of one another are a hydrogen group, a monovalent saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, or together are a bivalent alkylene group having 3 to 6 carbon atoms.
  • the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, in particular a methyl or butyl group. These have the advantage that the complex compound thus tends to be liquid or easily soluble.
  • the monovalent unsaturated hydrocarbon group is preferably also an aryl group, and more particularly a phenyl group.
  • R 2 is particularly preferably a hydrogen group, since the complex compound thus tends to be particularly stable.
  • a bivalent alkylene group having 3 to 6 carbon atoms shall be understood to mean a group with the formula —(CH 2 ) n —, where n is 3 to 6.
  • R 1 and R 2 together preferably form a bivalent alkylene group having 3 to 4 carbon atoms, and more particularly having 3 carbon atoms.
  • R 3 and R 4 independently of one another are a hydrogen group, a monovalent saturated hydrocarbon group, which optionally includes heteroatoms, having 1 to 12 carbon atoms, or together are a bivalent alkylene group, which optionally includes heteroatoms, having 3 to 6 carbon atoms.
  • the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably a methyl, an ethyl, a propyl, an isopropyl, a butyl, an isobutyl, a hexyl, a 2-methyl-pentyl, an octyl or a 2-ethyl-hexyl group.
  • the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms can preferably also be a cycloalkyl group having 5 to 6 carbon atoms, and particularly preferably 6 carbon atoms.
  • the monovalent saturated hydrocarbon group including heteroatoms is preferably a hydroxyalkyl group having 1 to 4 carbon atoms, and particularly preferably a 2-hydroxyethyl or 2-hydroxypropyl group.
  • This has the advantage that the complex compound thus tends to be liquid or easily soluble and the ligand can be covalently incorporated into the polymer during curing.
  • An alkyl ether group having 1 to 4 carbon atoms is also preferred, a 2-methoxyethyl or a 2-(2-methoxy)ethoxyethyl group being particularly preferred, since the complex compound thus tends to be liquid or easily soluble.
  • the selection of the preferred groups in the ligands L with the formula (I) is preferably based on the aspect that the corresponding 1,3-ketoamides, which are used as starting materials for producing the bismuth-containing catalyst according to the invention, are easy to produce and/or commercially available and thus inexpensive.
  • the bismuth-containing catalyst according to the invention preferably has the formula Bi(L) x (Y) 3-x , in which x is 1, 2 or 3, y is a singly negative ligand, and L is a ligand with the formula (I).
  • the bismuth-containing catalyst is produced by reacting at least one bismuth(III) salt or bismuth(III) complex with at least one 1,3-ketoamide with the formula (I),
  • R 1 , R 2 , R 3 and R 4 are as defined above.
  • a bismuth(III) carboxylate in particular bismuth(III) neodecanoate or bismuth(III)-2-ethylhexanoate, is preferred.
  • the at least one bismuth(III) salt or the at least one bismuth(III) complex and the at least one 1,3-ketoamide with the formula (I) are mixed, and the mixture is heated to a temperature of 50 to 130° C., preferably approximately 80° C., preferably while stirring for 1 to 24 hours, preferably approximately 2 hours.
  • the reaction mixture is thereafter preferably cooled, preferably to room temperature.
  • the bismuth-containing catalyst according to the invention can be used as a catalyst for curable compounds, preferably for polyurethane compositions.
  • the bismuth-containing catalyst according to the invention accelerates the curing of curable compounds that include reactive groups capable of cross-linking reactions.
  • the curable compounds can have single-component or multi-component formulations.
  • the bismuth-containing catalyst according to the invention preferably accelerates the curing of two-component polyurethane compositions, which cross-link with one another and optionally under the effect of moisture via blocked or in particular free isocyanate groups. This accelerates in particular the urethanization reaction, which is to say the reaction of isocyanate groups with alcohol OH groups.
  • the compositions to be cross-linked may also include further reactive groups capable of cross-linking reactions, such as in particular alkoxysilane groups. These are preferably trialkoxysilane groups, as they can be found in silane adhesive promoters, for example.
  • the bismuth-containing catalyst according to the invention can advantageously be employed as a catalyst in a two-component polyurethane composition.
  • this composition includes a polyol as the first component and a polyisocyanate as the second component.
  • two-component denotes a composition in which the constituents of the same are present in two different components, which are stored in separate containers and which on their own are storage stable in each case.
  • the two components are not mixed with each other until just prior to or during the application of the composition, whereupon the mixed composition cures, curing in some circumstances only taking place or being completed under the action of moisture and/or an elevated temperature.
  • polyisocyanate comprises compounds having two or more isocyanate groups, regardless of whether these are monomeric diisocyanates, oligomeric polyisocyanates or polymers comprising isocyanate groups.
  • a suitable polyisocyanate for example, is a polyisocyanate in the form of a monomeric diisocyanate or triisocyanate or an oligomer of a monomeric diisocyanate or a derivative of a monomeric diisocyanate.
  • Preferred polyisocyanates are commercially available diisocyanates. Particularly preferred are HDI, IPDI, TDI and MDI as well as oligomers of diisocyanates and isocyanate group-comprising polyurethane polymers (NCO prepolymers).
  • polyols for example, the following commercially available polyols, or mixtures thereof, can be used as polyols:
  • the above-mentioned polyols preferably have an average molecular weight of 250 to 30,000 g/mol, in particular of 400 to 20,000 g/mol, and further preferably have an average OH functionality in the range of 1.6 to 3.
  • molecular weight of oligomers or polymers is always understood to mean the number average molecular weight M n .
  • polyether polyols is particularly preferred, preferably polypropylene polyols and mixed polyethylene polypropylene polyols, and polyester polyols and polycarbonate polyols.
  • the bismuth-containing catalyst according to the invention is preferably present in the first component, which has the advantage that the storage stability (shelf life) of the polyisocyanate, which is sensitive to catalytically acting compounds, in the second component is not impaired.
  • the bismuth-containing catalyst according to the invention can be used as a catalyst alone or together with other catalysts, such as bismuth, tin or zirconium compounds or tertiary amines, for example.
  • the bismuth-containing catalyst according to the invention can optionally comprise further customarily used auxiliary substances and additives, such as pigments, plasticizers or diluents, curing agents, cross-linking agents, chain extenders, further catalysts, adhesive promoters, stabilizers, rheology additives and drying agents, and the like.
  • auxiliary substances and additives such as pigments, plasticizers or diluents, curing agents, cross-linking agents, chain extenders, further catalysts, adhesive promoters, stabilizers, rheology additives and drying agents, and the like.
  • the bismuth-containing catalyst according to the invention when considered in terms of the quantity of elemental bismuth, is preferably present in the two-component polyurethane composition according to the invention in a quantity of 0.0002 to 1% by weight, particularly preferably in a quantity of 0.001 to 0.2% by weight, and most preferably in a quantity of 0.002 to 0.1% by weight, based on the weight of the composition.
  • Excessively high quantities cause the open time or processing time of the composition to be too short, while the use of excessively low quantities has the disadvantage that the composition is poorly catalyzed and thus cures too slowly, incompletely and/or incorrectly.
  • the bismuth-containing catalyst according to the invention accounts for 0.001 to 5, preferably 0.005 to 1, and particularly preferably 0.01 to 0.5 mmol-equivalent bismuth atoms based on 100 g of the composition.
  • the bismuth-containing catalyst according to the invention is comparatively active and also comparatively selective with regard to the urethanization reaction.
  • the bismuth-containing catalyst according to the invention is characterized by high catalytic activity, even with extended storage.
  • the two-component polyurethane composition generally cures quickly.
  • the selectivity of the bismuth-containing catalyst according to the invention is not adversely affected by the increased activity; curing takes place without the formation of bubbles, even under unfavorable conditions, such as a high temperature, high ambient moisture or a high residual water content of the composition, and with the use of polyols comprising secondary OH groups or hydrophilic polyols.
  • the bismuth-containing catalyst according to the invention is comparatively stable both thermally and hydrolytically, decomposes only slowly even in a polyol having a residual water content, and thus maintains the catalytic activity thereof even with extended storage durations. Nonetheless, the use of the bismuth-containing catalyst according to the invention results in good stability of the cured polyurethane composition under thermal load. Moreover, at room temperature the bismuth-containing catalyst according to the invention is liquid and/or easily soluble in plasticizers or polyols and is thus easy to employ in systems that cure at room temperature, in particular without the use of volatile organic solvents (VOCs).
  • VOCs volatile organic solvents
  • the bismuth-containing catalyst according to the invention is colorless and also does not become discolored under the effect of light, so that it can also be used in unpigmented or light-colored products without admixing.
  • the polyurethane compositions cured with the bismuth-containing catalyst according to the invention exhibit good thermal resistance, despite their stability to hydrolysis, and do not tend more strongly toward discoloration than those cured with bismuth(III) carboxylates.
  • the two-component polyurethane composition according to the invention can be employed in many areas, for example as a casting compound, sealant, adhesive, covering, coating, paint, subcoating, rigid foam, flexible foam, molding, elastomer, fiber, film or membrane for building and industrial applications, for example as an electrical potting compound, knifing filler, seam sealant, cavity sealant, joint sealant, assembly adhesive, autobody adhesive, window adhesive, sandwich element adhesive, laminating adhesive, laminate adhesive, packaging adhesive, wood glue, parquet flooring adhesive, anchoring adhesive, floor covering and coating, balcony and roof coating, protective concrete coating, parking garage coating, pipe coating, anti-corrosive coating, textile coating, wood paint, decorative paint, primer, furniture foam, upholstery foam, filter foam, insulating foam, sound insulating foam, sealing foam, packaging foam, autobody foam, pattern plate, damping element, sealing element, tire, roller, bearing, cylinder, conveyor belt, elastic thread, shoe sole, housing, window casement section, implant, cellular rubber and the like.
  • Preferred fields of application are casting compounds, sealants, adhesives, coverings, coatings, paints, subcoatings, moldings and elastomers for building and industrial applications.
  • the bismuth-containing catalyst according to the invention can also be used in one-component polyurethane compositions.
  • these comprise at least one polyurethane prepolymer which have terminal isocyanate groups and are produced from at least one polyisocyanate and at least one polyol.
  • the polyurethane prepolymer is produced in the customary manner, as is described in EP 1 408 062 A1, for example.
  • the polyols employed for the production of the prepolymer are those described in EP 1 408 062 and above. The same applies to the polyisocyanates used for producing the polyurethane prepolymers.
  • the bismuth-containing catalyst according to the invention accounts for 0.02 to 5, preferably 0.1 to 2.5, and particularly preferably 0.2 to 1 mmol-equivalent bismuth atoms based on 100 g of the composition.
  • One-component polyurethane compositions comprising a bismuth-containing catalyst according to the invention typically have identical or similar advantages as the above-described two-component polyurethane compositions, in particular comparatively good storage stability and skinning times.
  • the fields of application of the one-component polyurethane composition according to the invention correspond to those of the applications described above in connection with the two-component polyurethane compositions.
  • the bismuth-containing catalyst according to the invention can also be used as a catalyst or co-catalyst in other curable compounds, such as in epoxy resins, acrylates and silicones.
  • Infrared spectra were measured on an FT-IR 1600 device made by Perkin-Elmer (horizontal ATR measuring unit with ZnSe crystal; measurement window 4000-650 cm ⁇ 1 ). Liquid samples were applied undiluted as films; solid samples were dissolved in CH 2 Cl 2 . The absorption bands are indicated in wavenumbers (cm ⁇ 1 ).
  • the viscosity was measured on a thermostated Physica MCR 300 cone and plate viscosimeter (cone diameter 20 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 0.1 to 100 s ⁇ 1 ).
  • UV-vis spectra of samples dissolved in dichloromethane (40 mg/l) in 1 cm quartz cuvettes were measured on a spectrometer of the type Varian Cary 50 in the wavelength range of 800 to 200 nm. Indicated are the absorbance maxima ⁇ max in nm and, in parentheses, the related molar extinction coefficients ⁇ in l ⁇ g ⁇ 1 ⁇ cm ⁇ 1 .
  • Coscat® 83 bismuth(III) tris(neodecanoate) in neodecanoic acid; 16% Bi; from Erbslöh
  • 2.85 g N,N-diethyl-3-oxobutanamide were reacted. This yielded a pale yellow oil.
  • FT-IR 2957, 2933, 2873, 1722, 1698, 1636, 1606, 1545, 1462, 1381, 1361, 1313, 1272, 1217, 1162, 1098, 1080, 942, 907, 872, 826, 789.
  • UV-vis 258 (0.5). (see Coscat® 83: 267(0.3).)
  • FT-IR 2958, 2931, 2872, 1722, 1636, 1605, 1460, 1381, 1360, 1313, 1272, 1217, 1148, 1098, 1080, 942, 921, 826, 774, 730.
  • NeoBi 200BA bismuth(III) tris(neodecanoate) in neodecanoic acid; 20% Bi; from Shepherd
  • 5.98 g N,N-diethyl-3-oxobutanamide were reacted. This yielded a pale yellow oil.
  • FT-IR 2960, 2931, 2874, 1720, 1635, 1593, 1490, 1461, 1390, 1359, 1312, 1272, 1220, 1199, 1148, 1098, 1080, 1007, 942, 919, 826, 774, 728.
  • FT-IR 2957, 2930, 2872, 1721, 1635, 1605, 1490, 1461, 1362, 1293, 1226, 1159, 931, 773, 732.
  • FT-IR 2956, 2930, 2872, 1717, 1630, 1607, 1489, 1464, 1378, 1292, 1255, 1222, 1146, 932, 817, 775, 731.
  • FT-IR 2957, 2927, 2872, 1698, 1632, 1602, 1546, 1461, 1380, 1359, 1232, 1159, 1006, 934, 818, 773, 728.
  • FT-IR 2957, 2928, 2872, 1740, 1698, 1640, 1606, 1546, 1536, 1460, 1379, 1216, 1149, 1108, 1003, 935, 904, 872, 833, 766, 728.
  • FT-IR 2957, 2931, 2871, 1736, 1695, 1599, 1575, 1484, 1466, 1366, 1292, 1215, 1153, 1085, 1000, 942, 907, 874, 817, 764, 716, 688.
  • a polyether triol (Voranol® CP 4755, from Dow) and a catalyst according to Table 1 were homogeneously mixed in a centrifugal mixer (SpeedMixerTM DAC 150, FlackTek Inc.) for 30 seconds at 3000 rpm for each example.
  • a portion of the freshly prepared first component was then filled into an aluminum tube coated on the inside, the tube was hermetically sealed and stored for 7 days in a circulating air oven at 60° C.
  • the remaining portion of the freshly prepared first component was mixed for each example in the described manner with a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature, as the second component in accordance with Table 1 to form a polyurethane composition.
  • a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature
  • the first component which had been stored for 7 days at 60° C., was likewise mixed with the second component in accordance with Table 1 in the same manner to form a polyurethane composition.
  • the polyurethane compositions were tested with respect to aspect ratio, color, tack-free time, bubble formation and Shore A hardness, in each case both for the composition comprising the freshly prepared first component and for the composition comprising the first component that had been stored for 7 days at 60° C. Thereafter the mechanical properties were also measured in a tensile test, only for the composition comprising the freshly prepared first component, in particular before and after various storage conditions for accelerated aging of the samples.
  • the aspect ratio and the color of the composition were evaluated purely visually, the aspect ratio being assessed as “clear”, “cloudy” or inhomogeneous (“inh.”).
  • the compositions having room temperature were applied to cardboard in a layer thickness of approximately 3 mm and, in a standard climate (“SC”; 23 ⁇ 1° C., 50 ⁇ 5% relative humidity), in each case the time was determined that passed until no residue remained on a pipette made of LDPE when the surface of a composition was lightly tapped by way of the pipette.
  • SC standard climate
  • bubbles were visually assessed based on the number (“many”, “some”, “none”) of gas bubbles that developed during curing in the composition that was prepared for determining the skinning time.
  • the Shore A hardness was determined according to DIN 53505 on specimen that were cured for 7 days in a standard climate.
  • dumbbells measuring 75 mm in length, having a web length of 30 mm and a web width of 4 mm, were punched out of the films, and some of these were tested in accordance with DIN EN 53504 for tensile strength, elongation at break and the modulus of elasticity (at 0.5 to 5.0% elongation) at a pulling speed of 200 mm/min. The remaining dumbbells were stored for 1 day at 100° C.
  • Composition comprising stored first component: Aspect ratio clear clear clear clear clear clear inh. Clear Color color- color- color- color- color- deep- color- less less less less yellow less Skinning time (min.) 15 12 20 82 205 12 45 Shore A hardness 47 47 44 46 47 48 45 Bubble formation none none none none none none none some
  • the two-component polyurethane compositions comprising the catalysts according to the invention represent clear, homogeneous mixtures, which have comparatively short skinning times, both before and after storage, and cure without bubbles, resulting in a material having comparatively high strength and good resistance.
  • a polyether triol (Voranol® CP 4755, from Dow), a polyether diol (Acclaim® 4200, from Bayer) and a catalyst according to Table 3 were homogeneously mixed in a centrifugal mixer (SpeedMixerTM DAC 150, FlackTek Inc.) for 30 seconds at 3000 rpm for each example.
  • a portion of the freshly prepared first component was then filled into an aluminum tube coated on the inside, the tube was hermetically sealed and stored for 7 days in a circulating air oven at 60° C.
  • the remaining portion of the freshly prepared first component was mixed for each example in the described manner with a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature, as the second component in accordance with Table 3 to form a polyurethane composition.
  • a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature
  • the first component which had been stored for 7 days at 60° C., was likewise mixed with the second component in accordance with Table 3 in the same manner to form a polyurethane composition.
  • polyurethane compositions were tested as described for Example 9 with respect to aspect ratio, tack-free time, bubble formation and the mechanical properties in a tensile test, in each case only for the composition comprising the freshly prepared first component.
  • Composition comprising stored first component: Aspect ratio clear clear inh. clear clear clear clear Skinning time (min.) 25 55 120 270 35 210 >240 Bubble formation none none none none none some many
  • the two-component polyurethane compositions comprising the catalysts according to the invention represent clear, homogeneous mixtures, which have comparatively short skinning times and cure without bubbles, resulting in a material having comparatively high strength and good resistance.
  • Example 9 in each case a polyether triol (Voranol® CP 4755, from Dow) and a catalyst were mixed in accordance with Table 5 to produce the first component. A portion of the freshly prepared first component was then filled into an aluminum tube coated on the inside, the tube was hermetically sealed and stored for 7 days in a circulating air oven at 60° C.
  • a polyether triol Voranol® CP 4755, from Dow
  • a catalyst were mixed in accordance with Table 5 to produce the first component.
  • a portion of the freshly prepared first component was then filled into an aluminum tube coated on the inside, the tube was hermetically sealed and stored for 7 days in a circulating air oven at 60° C.
  • Example 9 The remaining portion of the freshly prepared first component was mixed for each example in the manner described for Example 9 with a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature, as the second component in accordance with Table 5 to form a polyurethane composition.
  • a modified diphenylmethane diisocyanate (Desmodur® CD-L, from Bayer), which is liquid at room temperature, as the second component in accordance with Table 5 to form a polyurethane composition.
  • the first component which had been stored for 7 days at 60° C., was likewise mixed with the second component in accordance with Table 5 in the same manner to form a polyurethane composition.
  • polyurethane compositions were tested as described for Example 9 with respect to aspect ratio, tack-free time, bubble formation and Shore A hardness.
  • the two-component polyurethane compositions comprising the catalysts according to the invention represent clear, homogeneous mixtures, which have comparatively short skinning times, both before and after storage, and cure substantially without bubbles, resulting in a material having good Shore A hardness.
  • the polyurethane polymer P1 was produced as follows:
  • compositions thus obtained were tested for storage stability and curing speed.
  • the change of the viscosity during storage in heat was determined.
  • the storage stability is derived from the increase, in percent, of the second viscosity value as compared to the first.
  • the increase in viscosity in % is calculated according to the following formula: [(viscosity after 7 d/viscosity after 4 h) ⁇ 1] ⁇ 100%.
  • the compositions having room temperature were applied to cardboard in a layer thickness of approximately 3 mm and, in a standard climate (“SC”; 23 ⁇ 1° C., 50 ⁇ 5% relative humidity), in each case the time was determined that passed until no residue remained on a pipette made of LDPE when the surface of a composition was lightly tapped by way of the pipette.
  • Example 20 21 22 23 V11 V12 Polyurethane 30 30 30 30 30 30 30 polymer P1 Catalyst Example 0.63 — — — — — 6 Catalyst Example — 0.66 0.35 — — — 7 Catalyst Example — — — 0.59 — — 8 Coscat ® 83 a — — — — 0.37 — mmol-equiv.

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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2806001A1 (de) 2013-05-21 2014-11-26 PPG Industries Ohio Inc. Beschichtungszusammensetzung
IN2014DE02424A (de) * 2013-10-28 2015-07-10 Rohm & Haas
ES2964777T3 (es) * 2014-09-22 2024-04-09 Sika Tech Ag Adhesivo de poliuretano de curado por humedad con rápida formación de adhesivo sobre vidrio y estable durante el almacenamiento
EP3245238B1 (de) * 2015-01-13 2023-11-08 The Shepherd Chemical Company Polyurethankatalysatoren
CN110809589B (zh) 2017-06-30 2022-05-31 Sika技术股份公司 具有可调节适用期的双组分聚氨酯组合物
CN111133018B (zh) * 2017-09-26 2022-05-24 Sika技术股份公司 用于促进的粘附性构建的活化剂
DE112018004605A5 (de) * 2017-10-17 2020-05-28 Evonik Operations Gmbh Zinkketoiminatkomplexe als Katalysatoren zur Herstellung von Polyurethanen
US20210363366A1 (en) 2018-12-21 2021-11-25 Sika Technology Ag Method for the 3d printing of two-component polyurethane compositions
ES2964300T3 (es) 2018-12-21 2024-04-05 Sika Tech Ag Procedimiento para rellenar cavidades, juntas y huecos en un sustrato con un compuesto de colada de poliuretano de dos componentes con tiempo de encapsulado ajustable
WO2020160939A1 (de) * 2019-02-07 2020-08-13 Basf Se Bismuthaltiger katalysator umfassend mindestens einen aromatischen substituenten
CN113614136B (zh) * 2019-03-15 2024-01-09 巴斯夫涂料有限公司 基于具有空间体积大的取代基的含铋催化剂的涂料体系
JP7498478B2 (ja) 2019-05-17 2024-06-12 Ｋｊケミカルズ株式会社 不飽和ウレタン化合物の製造方法
JP2022553283A (ja) * 2019-10-28 2022-12-22 ダウ グローバル テクノロジーズ エルエルシー ポリオレフィン系積層用接着剤組成物およびリサイクルが可能な積層物
WO2021191045A1 (de) 2020-03-25 2021-09-30 Sika Technology Ag Zweikomponentige polyurethanzusammensetzung mit hoher hydrophobie und einstellbarer topfzeit
CN111393481B (zh) * 2020-04-07 2023-07-11 上海拜乐新材料科技有限公司 一种三苯基二酸铋化合物的制备方法及其在聚氨酯中的应用
DE102020211572A1 (de) 2020-09-15 2022-03-17 Benecke-Kaliko Aktiengesellschaft Reaktivmasse zur Herstellung von Polyurethanschichten mit thermisch aktivierbaren Katalysatorsystemen
US20230406993A1 (en) 2021-02-02 2023-12-21 Sika Technology Ag Two-component polyurethane filler having an adjustable pot life

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4584362A (en) 1985-02-27 1986-04-22 Cosan Chemical Corporation Bismuth catalyst system for preparing polyurethane elastomers
US5719229A (en) 1995-12-28 1998-02-17 Bayer Corporation Process for preparing solid elastomeric polyurethanes having reduced surface skinning
EP1408062A1 (de) 2002-10-08 2004-04-14 Sika Technology AG Bismutkatalysierte Polyurethanzusammensetzung
JP2005068402A (ja) 2003-08-06 2005-03-17 Konishi Co Ltd ２成分形ポリウレタン系シーリング材
WO2007003966A1 (en) * 2005-07-04 2007-01-11 Johnson Matthey Plc Novel zirconium compound, catalyst and its use for polyurethane manufacture
WO2009050115A1 (en) 2007-10-17 2009-04-23 Basf Se Photolatent catalysts based on organometallic compounds
US20140303321A1 (en) * 2011-12-12 2014-10-09 Sika Technology Ag Metal complex compounds as catalysts for polyurethane compositions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1314552B1 (de) * 1998-04-06 2009-08-05 FUJIFILM Corporation Photoempfindliche Harzzusammensetzung
JP4538317B2 (ja) * 2002-06-21 2010-09-08 ビーエーエスエフ ソシエタス・ヨーロピア 微細発泡性又は無発泡性の光安定性ポリウレタン材料及びその製造方法
GB0329272D0 (en) * 2003-12-18 2004-01-21 Johnson Matthey Plc Catalyst and method of making polyurethane materials
CN103172800B (zh) * 2006-07-06 2016-04-20 帝斯曼知识产权资产管理有限公司 不饱和聚酯树脂或乙烯基酯树脂组合物
EP1975189A1 (de) * 2007-03-27 2008-10-01 Sika Technology AG Polyurethanzusammensetzung enthaltend asymmetrisches Dialdimin
PA8785001A1 (es) * 2007-06-18 2008-06-17 Johnson Matthey Plc Compuestos estables en agua, catalizadores y reacciones catalizadas novedosos
EP2072551A1 (de) * 2007-12-21 2009-06-24 Sika Technology AG Aldimin enthaltende Primerzusammensetzung
BRPI0922127A2 (pt) * 2008-12-23 2016-09-06 Segetis Inc composto, formulação, artigo, polímero e método para fabricar poliamida.
BR112012023780A2 (pt) * 2010-03-23 2018-07-24 Vifor (International) Ag compostos complexos de ferro (iii) - b - cetoamida ou sais farmaceuticamente toleráveis desses, processo para a produção dos compostos complexos de ferro (iii), uso de compostos complexos de ferro (iii), fármaco contendo compostos complexos de ferro (iii) e composição contendo compostos complexos de ferro (iii)
EP2604616A1 (de) * 2011-12-12 2013-06-19 Sika Technology AG Dioxomolybdän(VI)-Komplexverbindungen als Katalysatoren für Polyurethan-Zusammensetzungen

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4584362A (en) 1985-02-27 1986-04-22 Cosan Chemical Corporation Bismuth catalyst system for preparing polyurethane elastomers
US4584362B1 (de) 1985-02-27 1990-03-13 Cosan Chem Corp
US5719229A (en) 1995-12-28 1998-02-17 Bayer Corporation Process for preparing solid elastomeric polyurethanes having reduced surface skinning
EP1408062A1 (de) 2002-10-08 2004-04-14 Sika Technology AG Bismutkatalysierte Polyurethanzusammensetzung
WO2004033519A1 (de) 2002-10-08 2004-04-22 Sika Technology Ag Bismutkatalysierte polyurethanzusammensetzung
US8299201B2 (en) 2002-10-08 2012-10-30 Sika Technology Ag Bismuth-catalyzed polyurethane composition
JP2005068402A (ja) 2003-08-06 2005-03-17 Konishi Co Ltd ２成分形ポリウレタン系シーリング材
WO2007003966A1 (en) * 2005-07-04 2007-01-11 Johnson Matthey Plc Novel zirconium compound, catalyst and its use for polyurethane manufacture
WO2009050115A1 (en) 2007-10-17 2009-04-23 Basf Se Photolatent catalysts based on organometallic compounds
US20140303321A1 (en) * 2011-12-12 2014-10-09 Sika Technology Ag Metal complex compounds as catalysts for polyurethane compositions

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Apr. 18, 2016 Office Action issued in Chinese Patent Application No. 201280060790.1.
CHEMICAL ABSTRACTS, 10 November 2004, Columbus, Ohio, US; INAGAWA TAKATOSHI, YOKOYAMA KAZUHIRO, TAKAHASHI TOSHIFUMI: "Two-component polyurethane system sealing materials with long pot life" XP002670528
Inagawa et al., "Two-Component Polyurethane System Sealing Materials with Long Pot Life," Database CA [Online], Chemical Abstracts Service, Columbus, Ohio, US, 2004, XP002670528.
International Preliminary Report on Patentability issued in International Patent Application No. PCT/EP2012/075205 dated Jun. 17, 2014.
International Search Report issued in International Patent Application No. PCT/EP2012/075205 dated Jan. 30, 2013.
Jul. 26, 2016 Office Action issued in Japanese Patent Application No. 2014-546476.
Jul. 5, 2017 Office Action issued in Chinese Application No. 201280060790.1.
Nov. 16, 2016 Office Action issued in Russian Patent Application No. 2014118879/04.
Oct. 14, 2016 Office Action issued in Chinese Application No. 201280060790.1.

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US20140343226A1 (en) 2014-11-20
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BR112014012300A2 (pt) 2017-05-30
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